Quaternary ammonium compounds and their manufacture



Patented June 30, 1953 QUATERNARY AMMONIUM COMPOUNDS AND THEIRMANUFACTURE Hans Gysin and Rudolf Edward Hagenbach, Basel, Switzerland,assignors to J. R. Geigy A. G., Basel, Switzerland, a Swiss firm NoDrawing. Application February 2, 1951, Serial No. 209,210. InSwitzerland February 24, 1950 Claims. (01. 260-4045) According to thepresent invention, new quaternary ammonium compounds are provided havingthe general formula:

wherein R represents an alkyl radical with 7--15 C atoms,

Hal represents chlorine or bromine,

R represents a low alkyl radical, and

R." represents hydrogen, chlorine, bromine, an

alkyl or alkoxy radical, or more of these substituents.

It has been found that these compounds are distinguished from thepreviously known quaternary ammonium compounds by a very strongbactericidal activity and at the same time in contrast to the greaterpart of thelatter compounds,

the compounds according to the present invention also have the advantagethat they are mostly solid crystallised bodies and therefore come intoconsideration for a greater number of intended uses.

The new compounds can be produced by various related processes.

The basic amides of the general formula:

RCON CHa-CHzN cfls can be reacted with halogen acetanilides of thegeneral formula:

In these and all following formulae, R, Hal, R, and R." always have themeanings given above.

Also, compoundsof the general formula:

can be reacted in the autoclave with methyl chloride or methyl bromide.

The above reactions may take place in the wesence or absence'of suitablesolvents such as benzene, toluene, xylene, acetone, ethyl and butylacetate and also water, and may be simplified if required by theaddition of small amounts of potassium iodide.

The basic amides used in the first above reaction can be obtained forexample by heating higher fatty acids, in particular lauric acid ormyristic acid, or also palmitic acid, with low dimethylamino ethylalkylamines for a fairly long period. Derivatives of the free fattyacids, in particular acid halides or esters, may also be used.

In this reaction it is not necessary that the alkyl radical of the fattyacid should have a homogenous chain. Mixtures of higher fatty acids maybe used with advantage, as they result from the saponification ofvegetable and animal fats and oils. Such mixtures of fatty acids, e. g.from palm kernal fats, apart from fatty acids with an average alkylchain length of 11-13 carbon atoms, also contain small portions of lowerand higher fatty acids. By distilling once, these portions can beseparated and then a fatty acid mixture is obtained with an alkyl chainlength of substantially 11-13 carbon atoms. The radical of this fattyacid mixture is referred to in the examples as Lauroyl radical.

Chloracetoand bromaceto anilide, -o-tolu"- dide, -mtoluidide,-p-toluidide, -o-anisidide, -manisidide, -p-anisidide, -'o-chloranilide,-in-chloranilide, -p-chloranilide, -p-bromanilide, -3.4-

dichloranilide, -2.4-dimethylanilide and -2.5-dimethylanilide can benamed as examples of halogen acetanilides of the general formula:

Hal-OHz-CO-NHQ medical instruments, patients personal and bed linen. Thesolutions for use may be prepared in the usual way, e. g. by dilutingconcentrated solutions or also by direct dissolution of the solidcompounds in water. For this latter purpose the new compounds may alsobe prepared in tablet form. Further, they can also be adapted forvarious intended uses by the addition of other materials with adisinfectant action, such as phenols, or of rust-proofing agents such assodium nitrite or sodium salt of octyloxyacetic acid. They can also becombined with pulverulent substances or with organic solvents and alsoincorporated in ointments and pastes. The disinfectant action isexcellent both against gram positive and gram negative germs such asstaphylococci, and bacterium coli, typhus, paratyphus B', bacteriumpyocyaneum, enteritis-Gartner, etc. respectively.

As result of the capillary ante pro erties of the new compounds, theyalso come into consideration as Wetting and dispersing agents for.various technical purposes, for example in the leather, paper andtextile industries.

The following examples serve to illustrate the invention. Parts arealways given as parts by.

weight and temperaturesare in' degreescenti grade. 7 I 3 Examplel 28parts of dodecanoyl N.N dimethylamino ethyl-N-methyl amide (boilingpoint 1510-160? at 0.3 mm. pressure) produced, for example from lauricacid. and trimethyl ethylenecliamine, are

"boiled for 6. hours underreflux with 169.5 parts of chloracetanilide-in800 parts of ethyl acetate. The precipitate which forms on standing isdrawn off by suction. (Dodecanoyl-N-methyl-aminoethyl).(phenylcarbamyl-methyl) -dimethyl ammonium chloride is obtained'onrecrystallization from acetone'as 'a White substance. It melts at 124and is completely soluble inwater.

is produced inlan I i The corresponding bromide analogous manner." V

7 Example 2 298 parts of dodecanoyl-N.N-dimethylaminoethyl-N-ethy1amideand 183.5 parts of chloraceto-p-toluidide are heated for 8 hours underreflux with 700 parts of benzene. The benzene ,is distilled oiT and thesolid residue is recrystalethy1-N-propylamide (B. P. 130150 at 0.3 mm.pressure), prepared for example from lauric acid methylester andN.N-dimethyl'-N-propyl-ethyl@- enediamine, are heated for 12 hours in aboiling Water bath While stirring with 169.5 parts of chloracetanilide.After cooling, the solid mass is recrystallized from ethylacetate/acetone.

(Dodecanoyl N-propylamino ethyD-(phenylcarbamylmethyD-dimethyl ammoniumchloride is obtained as 'a White crystalline substance. It melts at 135and is completely'soluble in water.

The corresponding bromide is produced in an analogous manner.

The following compounds may pared inthe above described manner:

( Dodecanoyl-N' -methylamino ethyl) (pechloroalso be pre Lphenylcarbamylmethyl) dimethyl ammonium chloride, M. P. 116. (DodecanoylN-ethy1amino ethyl) -(phenylcar'- bamylmethyl)'-dimethyl ammoniumchloride.

M. P. 164. A (Dodecanoyl-N'-propylamino ethyl) -(p-toly1carbamylmethyl)dirnethyl ammonium chloride.

(Lauroy1-N-methylamino ethyl) (phenylcarbamylmethyl) -dimethyl ammoniumchloride. M. P. about 110.

(Dodecanoyl N methylaminoethyl) -(p-methoxyphenylcarbamylmethyl)dimethyl ammomum.

Whatweclaimis: v,

mula

l. A quaternary ammonium'chloride of the for r mula:

wherein R represents an alkyl chain of from 9 to 15 carbon'atoms,

R." represents an alkyl radical of from 1 to 3 carbon atoms,

R represents a substituent selected. from the group consisting ofhydrogen, chlorine, methyl and methoxy. r

2. A quaternary ammonium chloride of the formula:

C11H23C OI?'--CHQQHQN A quaternary ammonium chloride of the for- C2115CH3 41A quaternary ammonium chloride ofthefor- CH3 CH3 wherein Rrepresents an alkyl chain of from 11 to 13 carbon atoms.

5. A quaternary ammonium chloride of the formula:

HANS GYSIN. I RUDOLF EDWARD HAGENBACH.

References Cited in the file of this patent UNITED STATES PATENTS NumberName 'Date 1,737,458 Hartmann et a1. Nov. 26, 1929 2,345,570 Bley Apr.4, 1944 2,459,062

Cook Jan. 11, 1 949

